A methodology for controlling the nanoscale architecture of etched silicon was developed though the printing of mixed monolayers. Contact printing of mixed solutions of different mole fractions of DTS and octyltrichlorosilane (OCTY) were formed monolayers on Si. Once annealed in air, these films were placed into KOH etching solutions and the resulting grain structures were examined via AFM. The data showed that different mole fractions created different grain structures after exposure to the etching solution. Additionally, the resulting etch structures were tested for photoluminescence, though only weak PL was found.